Novel nickel containing substances and their use as polmerisation catalysts in preparation of polyolefins



United States Patent F 3,414,555 I NOVEL NICKEL CONTAINING SUBSTANCES AND THEIR USE AS POLMERISATION CATALYSTS IN PREPARATION OF POLYOLEFINS Derek Keith Jenkins, Southampton, and Donald George Timms, East Boldre, England, assignors to The International Synthetic Rubber Company Limited, Southampton, England, a corporation of the United Kingdom No Drawing. Filed Nov. 23, 1965, Ser. No. 509,423 Claims priority, application Great Britain, Nov. 24, 1964, 48,304/ 64 9 Claims. (Cl. 260-94.3)

ABSTRACT OF THE DISCLOSURE An olefin polymerization catalyst comprising the reaction product of a zerovalent nickel-phosphorus compound of the formula Ni(PA B wherein A is alkyl, cycloalkyl, aryl, substituted aryl, substituted alkyl, alkoxy, aryloxy or hydrogen; B is halogen or psuedo halogen; and x is a whole number in the range 0-3, and, a transition metal compound containing at least one halogen-tometal bond, and optionally, a transition-metal-free Lewis acid.

The present invention relates to new substances haying catalytic properties in the polymerisations of olefin s', including mono-"olefins, especially those containing polar groups, e.g. butyl vinyl ether, and conjugated diolefins, particularly butadiene and isoprene.

It is known that catalysts for the polymerisation of conjugated diolefins may be made by reacting a transitionmetal compound with a compound containing metalcarbon and/ or metal-hydrogen bonds. This method forms the basis of the Ziegler catalyst systems. Such catalyst systems may be used to obtain polymers having a high cis-l,4 content. It has also been shown that similar catalysts may be made by reacting metal carbonyls with organo-metallic compounds or Lewis acids.

In this specification a polymer having a high cis-l,4 content is taken to mean a polymer having a content of at least 80% of cis1,4 units.

It has now been discovered that certain nickel-phosphorus compounds may be combined with a compound of a transition metal, which may be a Lewis acid, and optionally with a transition-metalsfree Lewis acid, to provide new catalyst systems.

In this specification the term transition metal is intended to mean those metals which are regarded as having partly-filled d or f shells of extra-nuclear electrons.

The new substances may be prepared by combining a nickel-phosphorus compound having the general formula Ni(P.A B where A is an alkyl, cycloalkyl, aryl, substituted alkyl or aryl, alkoxy or aryloxy radical or a hydrogen atom, B is a halogen atom or a pseudo-halogen 3,414,555 Patented Dec. 3, 1968 radical, such as a cyano radical, and x is 0, 1, 2 or 3, with a compound of a transition metal which is preferably hydrocarbon-soluble and which contains at least one halogen-to-metal bond and optionally a transition-metalfree Lewis acid.

The composition formed by mixing the nickel-phosphorus compound with transition-metal compound and optionally Lewis acid is new and has valuable catalytic properties. The indications that a novel compound is formed on mixing are a colour change, some precipitation, and other changes in physical characteristics. Such a novel compound is included within the scope of the word substance used to define the catalyst system.

Specific examples of useful nickel-phophorus compounds are Ni(PCl Ni(PF Ni(PBr and Ni(PhPCl The transition-metal compounds which are particularly useful in connection with the present invention are, for example, titanium tetrachloride, vanadium tetrachloride, vanadyl trichloride, and molybdenum pentachloride.

The Lewis acids which are not transition-metal compounds include AlCl AlBr BF BF .Et O.

The invention includes within its scope a method of polymerisation of olefins, particularlyconjugated diolefins, and especially butadiene'or isoprene. The polymerisation can be carried out at a temperature between -3() C. and C., in the presence or absence of a solvent for the reactants, and in the presence of a catalyst system as 'hereinbefore defined. Various solvents may be used; thus pentane, hexane, hcptane, iso-octane, petroleum ether, alkylates, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, tetralin, 'b'utenes, pentenes and chlorinated hydrocarbons are all satisfactory polymerisation media. The catalyst system may be prepared separately, or formed in situ, either from the nickel-phosphorus compound and the transition-metal compound and optionally Lewis acid, or from simpler compounds. A nickel-phosphorus compound Ni(PCl may be formed by reacting nickel carbonyl and phosphorus tric'hloride, and may then (e.g.) be reacted with AlCl and TiCl It is preferred to add the transition-metal compound and optionally Lewis acid to the polymerisation medium containing the nickel-phosphorus compound, rather than to add monomer to the fully-formed catalyst system, since in this way the yield of polymer can be increased.

In the polymerisation reaction, catalyst systems formed from the nickel-phosphorus compound and mixtures of Lewis acids are of particular value, since when such mixtures are used the formation of cross-linked gelled polymer can be eliminated, hindered or promoted at will. One suitable mixture of Lewis acids which may be mentioned is aluminum trichloride and titanium tetrachloride.

The Examples Nos. 1-20 given in the following table illustrate the present invention. The catalyst ingredients are shown in millimoles in the 2nd, 3rd and 4th columns of the table.

Catalyst ingredients Solvent, Monomer, Time, Tempera- Yield, ml. grams hours ture, 0. grams Structure Comments N i(PCl3)4 TiCh AlCl;

1 0. 5 0. 5 0. 5 Toluene 50 17 butadiene 17 20 17 no gel, 92% cis IV 'IiCh added after monosoluble. 0.65. mer, Ni(PC13)4, A101 mixed in toluene (Solvent) before monomer added.

22--. 0. 5 0. 5 0. 25 do 16 butadiene. 17 20 16 no gel, 94.5% els IV As (1).

soluble. 0.77.

3 0. 5 0. 5 do 14 butadieno" 25 14 gelled As (1) Some soluble polymer with gel.

4 0. 5 1. 20 16 gelled- As (3).

0. 0. 5 3 20 8 ins'olullile, Insloluble polymer. As

no go 6 0. 5 l. 0 17 20 8.5 soluble.--.. 88% cis As (1) Structure determined on soluble portion, which was rubbery.

7 0. 5 0. 5 0. 5 do 15 butadienm- 17 55 3 no gel, 91.5% cis IV As (1) Only partial soluble. 0.71. conversion.

8 0. 5 0. 5 0. 5 do 17 butadiene 17 0 15 no gel, 94% cis IV As (1).

soluble. 0.73. 9 0. 5 0. 5 0. 25 do .do 19 20 12 no gel, Catalyst components soluble. mixed before monov mer addition. 10. 0. 5 0. 5 do 16 butadiene- 17 20 0.7 no gel, 89% 015 Catalyst components soluble. mixed then monomer added. 11 0.5 0. 5 do do 17 55 0.5 no gel, As

soluble.

12 0.025 0.1 Hexane 100.. 25 butadienm- 17 20 14 9432?, eis IV 13 1.0 2. 0 2. 5 Benzene 100. 25 butyl vinyl 17 20 6 Elastic ether. polymer.

Ni(PC1a)-1 V0 013 AlCla 14 1. 0 0. 5 Toulene 50.. 8 isoprene-...- 3 20 8 insoluble Catalyst components mixed before monomet addition.

15... 1.0 0. 5 d0 .-d0. 3 ...d0 VOCla added after monomer. 16 1.0 0.5 0.5 do 16 butadiene.- 17 20 50 (0.7 g. gel) As (14).

Nurolm TiCh BF EtQO 17.. 0.5 0. 5 0.5 Hexane 50..- 13 butadiene.- 0. 5 13 micro gel 80% cis 1s 0.5 0.5 0.1 ..do ..do 0.5 25 do. 80% cis Ni(PhPClz)4 Tron A1013 19 0.5 0.5 0.25 do l7 butadiene--- 17 20 7 no gel As (1).

solub e.

Ni(PBra)4 TiCh A101 20-.- 0. 5 0. 5 0.25 Toluene 50 d0 17 20 14 no gel, 87% cis- As (1).

soluble.

We claim: 7. A catalyst as claimed in claim 2 derived from alu- 1. An olefin polymerization catalyst comprising the miniumtrichloride. reaction product of: 8. An olefin polymerisation process using a catalyst (a) A zerovalent nickel-phosphorus compound of the constituted by a reaction product as claimed in claim 1.

formula Ni(PA B where in A is alkyl, cyclo- 9. A process as claimed in claim 7 in which the polyalkyl, aryl, substituted aryl, substituted alkyl, alkoxy, merisation is carried out in a medium selected from the aryloxy, or hydrogen; B is halogen or psuedo halogen; group consisting essentially of pentane, hexane, heptane, and, x is a whole number in the range O-3; and, iso-octane, petroleum ether, alkylates, cyclohexane,

(b) A transition metal compound contamlng at least methylcyclohexane, benzene, toluene, xylene, decalin, one halogen-to-metal bond. tetralin, butenes, pentenes and chlorinated hydrocarbons.

2. The catalyst of claim 9 wherein a transition-metalfree Lewis acid is included as a reactant for said reaction References Cited product. r

3. A catalyst as claimed in claim 1 derived from the UNITED STATES PATENTS nickel-phosphorus compound Ni(PhPCl 4. A catalyst as claimed in claim 1 derived from a 3,066,125 11/1962 P rter, et a] 26() 94 3 nickel-phosphorus compound of the formula Ni(PX 3,228,917 1/1966 Chlldefs 260-841 where X is a halogen atom of atomic number lower than 3,328,443 6/ 1967 Clark, et a1. 260439 50.

5. A catalyst as claimed in claim 1 derived from titani- JOSEPH L SCHOFER Primary Examiner um tetrachloride.

6. A catalyst as claimed in claim 1 derived from R. A, GAI'IHER, Assistant Examiner, vanadium oxytrichloride, 

